Azo dyes from aminophthalimides and aniline, tetrahydroquinoline, and benzomorpholine couplers having thiosulfate groups

ABSTRACT

Disclosed are azo dyes suitable for coloring polyamide material, particularly nylon carpet and which are prepared from aminophthalimides and couplers which are ##STR1## substituted with a thiosulfate ester group. These dyes produce yellow to blue shades and also color cellulose acetate fabrics and wool. The dyes have the general formula: ##STR2## wherein R 2  and R 4  are each selected from hydrogen and a large variety of organic substituents, the coupler C is an aniline, 1,2,3,4-tetrahydroquinoline, or benzomorpholine derivative wherein a Q-SSO 3  M group is attached to the nitrogen thereof, Q being a lower alkylene or similar linking group, and M is Na + , K + , NH 4   + , or H + . The present dyes are superior in such properties as fastness to light, oxides of nitrogen, wash, ozone, sublimation, perspiration and crock, and exhibit good dyeability including migration, leveling, pH stability, and build.

This invention concerns azo dyes suitable for coloring polyamide material, particularly nylon carpet and which are prepared from aminophthalimides and couplers which are ##STR3## substituted with a thiosulfate ester group. These dyes produce yellow to blue shades and also color cellulose acetate fabrics and wool. The dyes have the general formula: ##STR4## wherein R² and R⁴ are each selected from hydrogen and a large variety of organic substituents, the coupler C is an aniline, 1,2,3,4-tetrahydroquinoline, or benzomorpholine derivative wherein a Q-SSO₃ M group is attached to the nitrogen thereof, Q being a lower alkylene or similar linking group, M is Na⁺, K⁺, NH₄ ⁺, or H⁺. The present dyes are superior in such properties as fastness to light, oxides of nitrogen, wash, ozone, sublimation, perspiration and crock, and exhibit good dyeability including migration, barre coverage, leveling, pH stability, and build. The unique combination of properties possessed by our novel compounds renders them superior to the compounds disclosed in Canadian Pat. No. 776,561, French Pat. No. 1,358,145, the Indian Journal of Technology, Vol. 9, pp. 175-178, Offenlegungsschrift No. 2,164,198, U.S. Pat. Nos. 2,245,971 and 4,039,522.

Our novel azo compounds are synthesized by diazotizing a 3- or 4-aminophthalimide having the formula ##STR5## and coupling the resulting diazonium salt with a coupler selected from those having the formulae ##STR6## according to conventional techniques. The 3-aminophthalimides in which R² is hydrogen, are prepared by reacting 3-nitrophthalic anhydride with ammonia followed by the reduction of the nitro group to the amino group whereas the analogous 4-amino compounds are prepared by reacting phthalic anhydride with ammonia followed by nitration and reduction. The corresponding aminophthalimide compounds in which R² is a substituent are prepared by the mentioned techniques except that a primary amine is substituted for the ammonia. Alternatively, the aminophthalimide compounds in which R² is a substituent can be prepared by reacting either phthalimide or a nitrophthalimide with an alkylating agent such as an aliphatic halide. The particular substituent represented by R² is, in general, not critical. The primary amines from which substituent R² can be derived have the formula R² --NH₂ in which R² is an unsubstituted or substituted aliphatic, alicyclic, aromatic or heterocyclic residue having a molecular weight of not more than about 200. In view of the vast number of primary amines and aliphatic halides which are known and/or can be synthesized by conventional procedures and since the substituent represented by R² is not critical, complete elaboration on the groups represented by R² is not practical. However, it is preferred that substituent R² be devoid of additional amino groups. Typical types of substituents in addition to hydrogen which R² can represent are as follows: alkyl; cyclohexyl; cyclohexyl substituted with alkyl; or alkyl substituted with alkoxy, aryl, aryloxy, cyclohexyl, cyano, alkanoyloxy, alkoxycarbonyl, alkoxycarbonyloxy, aroyloxy, alkylcarbamoyloxy, arylcarbamoyloxy, or with a group having the formula ##STR7## wherein R⁷ individually is hydrogen, alkyl or aryl;

R⁸ individually is hydrogen or alkyl;

R⁷ and R⁸ collectively are --(CH₂)₅ -- or --CH₂ CH₂ OCH₂ CH₂ --;

R⁹ is an acyl radical;

R¹⁰ is hydrogen, alkyl, aryl, or cyclohexyl;

R¹¹ is ethylene, propylene, trimethylene, o-cyclohexylene, or o-arylene, or when Y is --CO--, R¹¹ also can be --NHCH₂ --, --N(lower alkyl)CH₂ --, --SCH₂ --, --OCH₂ --, or --CH₂ OCH₂ --;

Y is --CH₂ --, --CO--, or --SO₂ --; and

R¹² is aryl, benzyl, cyclohexyl, 1,2,4-triazol-3-yl, or 2-benzothiazolyl.

R⁴ represents one or two substituents each of which is selected from hydrogen, halogen, cyano, alkyl, alkylsulfonyl, arylsulfonyl, arylthio, cyclohexylthio, alkoxy, aryloxy, 2-benzothiazolylthio, 2-thiazolylthio, 2-thiadiazolylthio, 2-oxadiazolylthio, 1,2,4-triazol-3-ylthio, and 2-pyrimidinylthio.

Ring A of each coupler may bear up to three substituents selected from alkyl, alkoxy, halogen, NHSO₂ -alkyl and NHCOR₁, wherein R₁ is hydrogen, alkyl, alkoxy, alkylamino, aryl, cyclohexyl or furyl; R₃ is selected from hydrogen; alkyl; alkyl substituted with alkoxy, alkoxyalkoxy, aryl, cycloalkyl, cyano, CONRR, SO₂ NRR, SO₃ M, aryloxy, cyclohexoxy, ##STR8## 2-pyrrolidono, furyl, alkylthio, or alkylsulfonyl wherein each R is independently selected from hydrogen, alkyl, and alkyl substituted with halogen, hydroxy, phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, or alkoxy, alkylcarbamoyl; alkenyl; aryl; cycloalkyl; and alkylcycloalkyl; R₅ and R₆ are selected from hydrogen and alkyl; m is 2, 3 or 4; each alkyl, alkylene, alkenyl, aryl and cycloalkyl moiety described herein may be substituted with up to three of halogen, OH, aryl, CN, alkoxy, alkanoyl, aroylamino, acylamino, alkanoyloxy, carbamoyl, alkylcarbamoyl, sulfamyl, alkylsulfonyl, succinimido, or alkoxycarbonyl groups; all of the alkyl, alkylene and alkenyl moieties within the above definitions for both the phthalimide and coupler components contain 1-6 carbons; Q is alkylene of 2-8 carbons which may contain in its chain or pendant therefrom one or more of the following groups: --O--, --SO₂ --, --S--, --OH, --OCOCH₃, --C₆ H₅, --N(SO₂ CH₃)--, --N(COCH₃)--, --NHSO₂ --, --N(CH₃)SO₂ --, --SO₂ NH--, --NHCOO--, --NHCO-- , --NHCONH--, --SO₃ K, and --N(SO₂ C₆ H₅)--; and M is hydrogen, Na⁺, K⁺, or NH₄ ⁺.

This invention will be further illustrated by the following examples although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention.

EXAMPLES of COUPLER PREPARATION EXAMPLE 1--Sodium S-2-[ethyl(3-methylphenyl)amino] ethyl thiosulfate

Sodium thiosulfate (49.6 g, 0.2 m), sodium iodide (1 g), N-2-chloroethyl-N-ethyl-m-toluidine (19.8 g, 0.1 m), and 200 ml water were mixed and heated at about 95° C. for about 1-1/2 hr. The reaction mixture was cooled to about 20° C. and filtered. The white solid was washed with hexane and dried in air. Yield was 26.0 g (87.5%).

EXAMPLE 2--Sodium S-2-(1,2,3,4-tetrahydro-2,2,4,7-tetramethyl-1-quinolinyl)ethyl thiosulfate

A mixture of sodium thiosulfate (49.6 g, 0.2 m), sodium iodide (1 g), N-(2-chloroethyl)-2,2,4,7-tetramethyl-1,2,3,4-tetrahydroquinoline (25.2 g, 0.1 m), water (100 ml), and ethanol (100 ml) was refluxed for 3 hrs. The mixture was cooled and extracted with two 75 ml portions of toluene. The aqueous layer then containing essentially pure product and aliquots were used to prepare dyes without further purification.

EXAMPLE 3--Sodium S-2(3,4-dihydro-3,6-dimethyl-2H-1,4-benzoxazine-4-yl)ethyl thiosulfate

Sodium thiosulfate (0.2 m), sodium iodide (1 g), N-(2-chloroethyl)-3,6-dimethyl-2H-1,4-benzoxazine (0.2 m), water (150 ml), and ethanol (75 ml) were mixed and heated at reflux for 3 hrs. The alcohol was distilled off and the reaction mixture was cooled. The product, a white solid, was collected by filtration and dried in air. The yield was essentially quantitative.

EXAMPLES 4-9--Aminophthalimide Preparations

To 2-aminoethanol (12.2 g.) is added portionwise at 100°-125° C. 4-nitrophthalic anhydride (38.6 g.) with manual stirring. The mixture is heated gradually to 150° C. and kept at 150°-160° C. for 1 hr. with occasional stirring. The reaction mixture is cooled slightly and 50 ml. of ethanol is added. This solution is then drowned into 200 ml. of water. The product, N-(2-hydroxyethyl)-4-nitrophthalimide, is collected by filtration, washed with water and dred in air. It melts and 118°-119° C. and weighs 30.0 g.

EXAMPLE 5

N-(2-Hydroxyethyl)-4-nitrophthalimide (30.0 g.), ethanol (300 ml.), and Raney nickel (3.0 g.) are mixed and hydrogenated at 100° C. and 1500 psi. until hydrogen uptake ceases. The hot solution is filtered to remove the Raney nickel and the solvent evaporated to yield 4-amino-N-(2-hydroxyethyl)-phthalimide, the amine which melts at 171°-173° C.

EXAMPLE 6

A mixture of 4-nitrophthalimide (38.4 g.), iodoethane (46.8 g.), potassium carbonate (27.6 g.), and N,N-dimethylformamide (200 ml.) are heated and stirred at 95°-100° C. for 2 hrs. An additional amount of iodoethane (46.8 g.) is added and the reaction mixture heated 4 hrs. longer at 95°-100° C. The reaction mixture is drowned into 1500 ml. of water. The product, N-ethyl-4-nitrophthalimide, is collected by filtration, washed with water and recrystallized from methanol. It melts at 113°-114° C.

EXAMPLE 7

N-Ethyl-4-nitrophthalimide (28.0 g.) is hydrogenated in 400 ml. of ethanol and in the presence of Raney nickel catalyst (10 g.) at 100° C. and 1500 psi. pressure. The reaction mixture is filtered to remove the catalyst and the filtrate is concentrated to yield the product, 4-amino-N-ethylphthalimide, which is recrystallized from methanol-water mixture. It melts at 169°-171° C.

EXAMPLE 8

3-Nitrophthalimide (30.0 g.) is ethylated with iodoethane in the same manner as the 4-nitro isomer (Example 3) to yield 35.4 g. of N-ethyl-3-nitrophthalimide melting at 102°-103° C.

EXAMPLE 9

N-Ethyl-nitrophthalimide (35.4 g.) is hydrogenated as in Example 4 to yield 22.5 g. of 3-amino-N-ethylphthalimide which melts at 134°-136° C.

EXAMPLE 10

Sodium nitrite (2.88 g.) is added gradually to 20 ml. of conc. H₂ SO₄. The solution is cooled and 1:5 acid (1 part by volume propionic acid to 5 parts by volume acetic acid) (40 ml.) is added below 15° C. To this mixture is added 4-amino-N-ethylphthalimide (7.6 g., 0.04 mole), followed by 40 ml. of 1:5 acid, all below 5° C. The reaction mixture is stirred at 0°-5° C. for 2 hrs. The following couplers (0.005 mole) are dissolved in 25 ml. of water.

To each chilled coupler solution is added a 0.005 mole aliquot of diazonium salt solution. The coupling mixtures are buffered by the addition of sodium acetate and allowed to stand for 1 hr. The coupling mixtures are diluted with water to total volume of about 200 ml. and the dyes are collected by filtration, washed with water and dried in air.

The azo compounds set forth in the following tables are prepared according to the synthesis techniques described herein and conform to the above formulae. The phthalimidyl diazo components of the compounds of the tables are bonded to the azo group at the 4-position unless otherwise indicated.

                                      TABLE I                                      __________________________________________________________________________      ##STR9##                                                                                     Substituents                                                    R.sup.2        on Ring A R.sup.3       Q             M  R.sup.4                __________________________________________________________________________     C.sub.2 H.sub.5                                                                               3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2                                                                            K  H                      C.sub.2 H.sub.5                                                                               3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2                                                                            K  H                      C.sub.2 H.sub.5                                                                               3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2                                                                            K  H                      C.sub.2 H.sub.5                                                                               3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2                                                                            K  H                      C.sub.2 H.sub.5                                                                               3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2                                                                            K  H                      C.sub.2 H.sub. 5                                                                              3-CH.sub.3                                                                               CH.sub.3      CH.sub.2 CH.sub.2                                                                            K  H                      C.sub.2 H.sub.5                                                                               3-CH.sub.3                                                                               CH.sub.3      CH.sub.2 CH.sub.2                                                                            K  H                      C.sub.2 H.sub.5                                                                               3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2                                                                            K  H                      H              3-Cl      C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2                                                                            K  H                      H              None      C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2                                                                            K  H                      (CH.sub.2).sub.3 CH.sub.3                                                                     2-OCH.sub.3, 5-CH.sub.3                                                                  H             CH.sub.2 CH.sub.2                                                                            K  CH.sub.3               (CH.sub.2).sub.3 CH.sub.3                                                                     2-Cl      H             CH.sub.2 CH.sub.2                                                                            K  OC.sub.2 H.sub.5       (CH.sub.2).sub.3 CH.sub.3                                                                     2-CH.sub.3                                                                               H             CH.sub.2 CH.sub.2                                                                            K  OC.sub.2 H.sub.5       (CH.sub.2).sub.3 CH.sub.3                                                                     2,5-di-CH.sub.3                                                                          H             CH.sub.2 CH.sub.2                                                                            K  H                      CH.sub.2 C.sub.6 H.sub.5                                                                      3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2                                                                            K  H                      CH.sub.2 C.sub.6 H.sub.5                                                                      3-NHCOCH.sub.3                                                                           C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2                                                                            K  H                      C.sub.2 H.sub.5                                                                               None      C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 CH.sub.2                                                                   Na H                      C.sub.2 H.sub.5                                                                               3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 CH.sub.2                                                                   Na H                      C.sub.2 H.sub.5                                                                               3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 CH.sub.2                                                                   Na H                      C.sub.2 H.sub.5                                                                               3-NHCOCH.sub.3                                                                           C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 CH.sub.2                                                                   Na H                      C.sub.2 H.sub.5                                                                               3-NHCOOC.sub.2 H.sub.5                                                                   C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 CH.sub.2                                                                   Na H                      C.sub.2 H.sub.5                                                                               3-NHCONHC.sub.2 H.sub.5                                                                  C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 CH.sub.2                                                                   Na CN                     C.sub.2 H.sub.5                                                                               3-NHSO.sub.2 CH.sub.3                                                                    C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 CH.sub.2                                                                   Na CN                     C.sub.2 H.sub.5                                                                               2-CH.sub.3,                                                                              C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 CH.sub.2                                                                   Na CN                                    5-NHCOCH.sub.3                                                  C.sub.2 H.sub.5                                                                               3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 CH.sub.2                                                                   Na Cl                     C.sub.2 H.sub.5                                                                               None      C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 CH.sub.2                                                                   Na Cl                     C.sub.2 H.sub.5                                                                               2-CH.sub.3,                                                                               C.sub.2 H.sub.5                                                                             CH.sub.2 CH.sub.2 CH.sub.2                                                                   Na Br                                    5-NHCOC.sub.6 H.sub.5                                           C.sub.2 H.sub.5                                                                               2,5-di-Cl H             CH.sub.2 CH.sub.2 CH.sub.2                                                                   Na Br                     C.sub.2 H.sub.5                                                                               None      C.sub.4 H.sub.9n                                                                             CH.sub.2 CH.sub.2                                                                            NH.sub.4                                                                          Br                     C.sub.2 H.sub.5                                                                               None      CH.sub.2 CH(CH.sub.3).sub.2                                                                  CH.sub.2 CH.sub.2                                                                            NH.sub.4                                                                          H                      C.sub.2 H.sub.5                                                                               3-CH.sub.3                                                                               CH(CH.sub.3)C.sub.4 H.sub.9                                                                  CH.sub.2 CH.sub.2                                                                            Na H                      CH.sub.2 C.sub.6 H.sub.11                                                                     3-CH.sub.3                                                                               C.sub.4 H.sub.9n                                                                             CH.sub.2 CH.sub.2                                                                            Na H                      CH.sub.2 C.sub.6 H.sub.11                                                                     3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2                                                                            Na H                      C.sub.6 H.sub.11                                                                              3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2                                                                            Na H                      C.sub.6 H.sub.11                                                                              3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2                                                                            Na H                      C.sub.6 H.sub.5                                                                               3-NHCOCH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.3                                                                   CH.sub.2 CH.sub.2                                                                            Na H                      C.sub.6 H.sub.5                                                                               3-NHCHO   CH.sub.2 CH.sub.2 CH.sub.3                                                                   CH.sub.2 CH.sub.2                                                                            Na H                      C.sub.6 H.sub.5                                                                               3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2                                                                            Na H                      (CH.sub.2).sub.3 OCH.sub.3                                                                    3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2                                                                            Na H                      (CH.sub.3).sub.3 OCH.sub.3                                                                    3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2                                                                            K  H                      CH.sub.2 CH.sub.2 OOCCH.sub.3                                                                 3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH(CH.sub.3)                                                                        K  H                      CH.sub.2 CH.sub.2 OOCCH.sub.3                                                                 3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 CH.sub.2                                                     CH.sub.2      K  OC.sub.6 H.sub.5       CH.sub.2 CH.sub.2 OH                                                                          3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2                                                                            K  H                       ##STR10##     3-NHCOCH.sub.2 OH                                                                        C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2                                                                            K  H                       ##STR11##     3-NHCOCH.sub.2 CN                                                                        H             CH.sub.2 CH.sub.2                                                                            K  H                      CH.sub.2 CH.sub.2 NHCOCH.sub.3                                                                3-NHCOCH.sub.2 OCH.sub.3                                                                 H             CH.sub.2 CH.sub.2                                                                            K  H                      CH.sub.2 C.sub.6 H.sub.4p-OCH.sub.3                                                           3-NHCOC.sub.6 H.sub.11                                                                   H             CH.sub.2 CH.sub.2                                                                            K  H                      CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                             3-CH.sub.3                                                                               CH.sub.2 CH.sub.2 CH.sub.3                                                                   CH.sub.2 CH.sub.2                                                                            K  SO.sub.2 CH.sub.3                                                              1                      CH.sub.2 CH.sub.2 CONH.sub.2                                                                  3-CH.sub.3                                                                               C.sub.6 H.sub.11                                                                             CH.sub.2 CH.sub.2                                                                            K  H                      CH.sub.2 CH.sub.2 CN                                                                          3-CH.sub.3                                                                               C.sub.2 H.sub.4 OH                                                                           CH.sub.2 CH.sub.2                                                                            K  H                      CH.sub.2 CH.sub.3                                                                             3-CH.sub.3                                                                               C.sub.2 H.sub.4 OCH.sub.3                                                                    CH.sub.2 CH.sub.2                                                                            K  H                      NCOCH.sub.2 CH.sub.2 CH.sub.2                                                                 3-CH.sub.3                                                                               C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCH.sub.2                                     CH.sub.3      CH.sub.2 CH.sub.2                                                                            K  H                      CH.sub.2 CH.sub.2 Cl                                                                          3-CH.sub.3                                                                               C.sub.2 H.sub.4 CN                                                                           CH.sub.2 CH.sub.2                                                                            K  SC.sub.6 H.sub.5       CH.sub.2 CH.sub.2 SO.sub.2 C.sub.6 H.sub.5                                                    H         C.sub.2 H.sub.4 CONH.sub.2                                                                    CH.sub.2 CH.sub.2                                                                           K  H                      CH.sub.2 CH.sub.2 NHSO.sub.2 CH.sub.3                                                         3-CH.sub.3                                                                               C.sub.2 H.sub.4 SO.sub.2 NH.sub.2                                                            CH.sub.2 CH.sub.2                                                                            K  H                      CH.sub.2 CH.sub.2 N(CH.sub.3)SO.sub.2 CH.sub.3                                                3-CH.sub.3                                                                               C.sub.2 H.sub.4 SO.sub.2 NHC.sub.2 H.sub.5                                                   CH.sub.2 CH.sub.2                                                                            K  H                      CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.3                                                  3-CH.sub.3                                                                               C.sub.2 H.sub.4 SO.sub.2 N(CH.sub.3).sub.2                                                   CH.sub.2 CH.sub.2                                                                            K  H                      CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.3                                                  3-CH.sub.3                                                                                ##STR12##    CH.sub.2 CH.sub.2                                                                            K  H                      C.sub.6 H.sub.4m-CH.sub.3                                                                     3-CH.sub.3                                                                               C.sub.2 H.sub.4 SO.sub.2 CH.sub.3                                                            CH.sub.2 CH.sub.2                                                                            K  SC.sub.2 H.sub.5       C.sub.6 H.sub.4m-Cl                                                                           3-CH.sub.3                                                                               CH.sub.2 C.sub.6 H.sub.11                                                                    CH.sub.2 CH.sub.2                                                                            K  H                      C.sub.6 H.sub.4p-OCH.sub.3                                                                    3-CH.sub.3                                                                                ##STR13##    CH.sub.2 CH.sub.2                                                                            K  H                      CH.sub.2 CH.sub.2 COOCH.sub.3                                                                 3-CH.sub.3                                                                                ##STR14##    CH.sub.2 CH.sub.2                                                                            K  H                      CH.sub.2 CH.sub.2 Br                                                                          3-CH.sub.3                                                                               CH.sub.2 CH.sub.2 CONHC.sub.2 H.sub.5                                                        CH.sub.2 CH.sub.2                                                                            K  H                      NCOo-C.sub.6 H.sub.4 CO                                                                       3-CH.sub.3                                                                               C.sub.6 H.sub.5                                                                              CH.sub.2 CH.sub.2                                                                            K  H                      CH.sub.2 CH.sub.2 Cl                                                                          3-CH.sub.3                                                                               CH.sub.2 CH(OH)CH.sub.3                                                                      CH.sub.2 CH.sub.2                                                                            K  H                      CH.sub.2 Br    3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH(OH)CH.sub.2                                                                      K  H                      CH.sub.2 CH.sub.2 OOCC.sub.6 H.sub.5                                                          3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH(SO.sub.3 K)CH.sub.2                                                              K  H                      CH.sub.2 CH.sub.2 OOCOC.sub.2 H.sub.5                                                         None      C.sub.2 H.sub.4 SO.sub.3 K                                                                   C.sub.2 H.sub.4                                                                              K  H                      CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                       None      C.sub.2 H.sub.5                                                                              CH.sub.2 CH(OCOCH.sub.3)CH.sub.2                                                             K  H                      CH.sub.2 CH.sub. 2 OH                                                                         None      C.sub.2 H.sub.5                                                                              CH.sub.2 CH(C.sub.6 H.sub.5)                                                                 K  2-benzo-                                                                       thia-                                                                          zolyl-                                                                         thio                   C.sub.6 H.sub.5                                                                               None      C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 OCH.sub.2                                                    CH.sub.2      K  H                      CH.sub.2 CH.sub.2 CN                                                                          None      C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 OCH.sub.2                                                    CH.sub.2 CH.sub.2 CH.sub.2                                                                   K  H                      n-C.sub.4 H.sub.9                                                                             3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 SO.sub.2                                                     CH.sub.2 CH.sub.2                                                                            Na H                      CH.sub.2 CH.sub.3                                                                             3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 SO.sub.2                                                     CH.sub.2 CH.sub.2                                                                            K  H                      CH.sub.2 OCH.sub.2 COOC.sub.2 H.sub.5                                                         2-CH.sub.3                                                                               SC.sub.2 H.sub.5                                                                             CH.sub.2 CH.sub.2 SO.sub.2                                                     CH.sub.2 CH.sub.2                                                                            K  H                      CH.sub.2 CH.sub.2 OC.sub.6 H.sub.5                                                            2-Cl      C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 SO.sub.2                                                     CH.sub.2 CH.sub.2                                                                            K  H                      CH.sub.2C.sub.6 H.sub.4p-COOCH.sub.3                                                          2-OCH.sub.3, 5-Cl                                                                        C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.                                             2 CH.sub.2    K  2-thia-                                                                        zolyl-                                                                         thio                   CH.sub.2 CHCH.sub.2                                                                           3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 SCH.sub.2                                                    CH.sub.2      K  H                      CH(CH.sub.3)C.sub.2 H.sub.5                                                                   3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                           CH.sub.2 CH.sub.2 N(SO.sub.2 CH.sub.3)                                         CH.sub.2 CH.sub.2                                                                               K  H                      CH.sub.2 COC.sub.6 H.sub.5                                                                    3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                           CH.sub.2 CH.sub.2 N(COCH.sub.3)CH.sub.                                         2 CH.sub.2       K  H                      C.sub.6 H.sub.4p-SO.sub.2 CH.sub.3                                                            3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                           CH.sub.2 CH.sub.2 N(SO.sub.2 C.sub.6                                           H.sub.5)CH.sub.2 CH.sub.2                                                                       NH.sub.4                                                                          H                      C.sub.6 H.sub.4p-NHCOCH.sub.3                                                                 3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                           CH.sub.2 CH.sub.2 CH.sub.2 N(SO.sub.2                                          C.sub.2 H.sub.5)CH.sub.2 CH.sub.2                                                               K  H                      CH.sub.2 C.sub.6 H.sub.10p-CH.sub.2 OH                                                        3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                           CH.sub.2 CH.sub.2 NHSO.sub.2 CH.sub.2                                          CH.sub.2         Na H                      C.sub.2 H.sub.5                                                                               3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                           CH.sub.2 CH.sub.2 N(CH.sub.2 (SO.sub.2                                          CH.sub.2 CH.sub.2                                                                              Na 2-thia-                                                    SO.sub.2 CH.sub.2 CH.sub.2                                                                         diazolyl-                                                                      thio                   C.sub.2 H.sub.5                                                                               3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 SO.sub.2                                                     NHCH.sub.2 CH.sub.2                                                                          Na H                      C.sub.2 H.sub.5                                                                               3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 NHCOCH.sub.2                                                 CH.sub.2      Na H                      C.sub.2 H.sub.5                                                                               3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 NHCOCH.sub.2                                                               Na H                      C.sub.2 H.sub.5                                                                               3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 CON(CH.sub.3)C.su                                            b.2 H.sub.4   Na H                      C.sub.2 H.sub.5                                                                               3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 CH.sub.2                                                     CH.sub.2      K  H                      C.sub.2 H.sub.5                                                                               3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 CH.sub.2                                                                   K  2-oxadia-                                                                      zolyl-                                                                         thio                   C.sub.2 H.sub.5                                                                               3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 OCH.sub.2                                                    CH.sub.2      Na H                      C.sub.2 H.sub.5                                                                               3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 SO.sub.2                                                     CH.sub.2 CH.sub.2                                                                            Na H                      C.sub.2 H.sub.5                                                                               3-Cl      C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 SO.sub.2                                                     CH.sub.2 CH.sub.2                                                                            Na H                      C.sub.2 H.sub.5                                                                               2,5-di-Cl H             CH.sub.2 CH.sub.2 SO.sub.2                                                     CH.sub.2 CH.sub.2                                                                            Na 2-Pyrimidi-                                                                    nyl-                                                                           thio                   C.sub.2 H.sub.5                                                                               3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 SO.sub.2                                                     CH.sub.2 CH.sub.2                                                                            Na H                      C.sub.2 H.sub.5                                                                               None      C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 SO.sub.2                                                     CH.sub.2 CH.sub.2                                                                            Na H                      C.sub.2 H.sub.5                                                                               None      C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 SO.sub.2                                                     CH.sub.2 CH.sub.2                                                                            Na H                      C.sub.2 H.sub.5                                                                               None      C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 SO.sub.2                                                     CH.sub.2 CH.sub.2                                                                            Na H                      C.sub.2 H.sub.5                                                                               None      C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 SO.sub.2                                                     CH.sub.2 CH.sub.2                                                                            Na H                      C.sub.2 H.sub.5                                                                               None      C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 SO.sub.2                                                     CH.sub.2 CH.sub.2                                                                            Na H                      C.sub.2 H.sub.5                                                                               None      C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 SO.sub.2                                                     CH.sub.2 CH.sub.2                                                                            Na H                      C.sub.2 H.sub.5                                                                               None      C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 SO.sub.2                                                     CH.sub.2 CH.sub.2                                                                            Na H                      C.sub.2 H.sub.5                                                                               None      C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 SO.sub.2                                                     CH.sub.2 CH.sub.2                                                                            Na H                      C.sub.2 H.sub.5                                                                               None      C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 NHCONHC.sub.2                                                H.sub.4       Na H                      C.sub.2 H.sub.5                                                                                ##STR15##                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2                                                                            K  H                      C.sub.2 H.sub.5                                                                               3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2                                                                            K  H                      C.sub.2 H.sub.5                                                                               3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2                                                                            K  H                      C.sub.2 H.sub.5                                                                               3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2                                                                            K  H                      C.sub.2 H.sub.5                                                                               3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2                                                                            K  H                      C.sub.2 H.sub.5                                                                               3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub. 2 CH.sub.2                                                                           K  H                      C.sub.2 H.sub.5                                                                               3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2                                                                            K  H                      C.sub.2 H.sub.5                                                                               3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2                                                                            K  H                      C.sub.2 H.sub.5                                                                               3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2                                                                            K  H                      C.sub.2 H.sub.5                                                                               3-CH.sub.3                                                                               C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2                                                                            K  H                      __________________________________________________________________________

                                      TABLE II                                     __________________________________________________________________________      ##STR16##                                                                                    Substituents                                                    R.sup.2         on Ring A  R.sup.5                                                                            R.sup.6                                                                            Q                   M  R.sup.4              __________________________________________________________________________     C.sub.2 H.sub.5                                                                               7-CH.sub.3  H   H   CH.sub.2 CH.sub.2   K  H                    C.sub.2 H.sub.5                                                                               7-CH.sub.3  CH.sub.3                                                                           H   CH.sub.2 CH.sub.2   K  H                    C.sub.2 H.sub.5                                                                               7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH.sub.2   K  H                    C.sub.2 H.sub.5                                                                               7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.                                                                          K  H                    C.sub.2 H.sub.5                                                                               7-CH.sub.3  CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.2 CH.sub.2   K  H                    H              7-CH.sub.3  CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.2 CH.sub.2   K  H                    H              7-CH.sub.3  H   H   CH.sub.2 CH.sub.2   K  H                    (CH.sub.2).sub.3 CH.sub.3                                                                     7-CH.sub.3  CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.2 CH.sub.2   K  H                    (CH.sub.2).sub.3 CH.sub.3                                                                     7-CH.sub.3  H   H   CH.sub.2 CH.sub.2   NH.sub.4                                                                          H                    CH.sub.2 C.sub.6 H.sub.5                                                                      7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.2                                                                         Na H                    CH.sub.2 C.sub.6 H.sub.5p-Cl                                                                  7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.2                                                                         Na CH.sub.3             C.sub.2 H.sub.5                                                                               7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                                Na OC.sub.2                                                                       H.sub.5              C.sub.2 H.sub.5                                                                               7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                               Na OC.sub.2                                                                       H.sub.5              C.sub.2 H.sub.5                                                                               7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2                                            CH.sub.2            Na H                    C.sub.2 H.sub.5                                                                               H           H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2                                            CH.sub.2            Na H                    C.sub.2 H.sub.5                                                                               7-Cl        H   CH.sub.3                                                                           CH.sub.2 CH.sub.2   Na H                    C.sub.2 H.sub.5                                                                               5,8-di-CH.sub.3                                                                            H   CH.sub.3                                                                           CH.sub.2 CH.sub.2   Na H                    C.sub.2 H.sub.5                                                                               5,8-di-OCH.sub.3                                                                           H   CH.sub.3                                                                           CH.sub.2 CH.sub.2   Na H                    C.sub.2 H.sub.5                                                                               5-OCH.sub.3, 8-CH.sub.3                                                                    H   CH.sub.3                                                                           CH.sub.2 CH.sub.2   Na H                    C.sub.2 H.sub.5                                                                               5-OCH.sub.3, 8-Cl                                                                          H   CH.sub.3                                                                           CH.sub.2 CH.sub.2   Na H                    C.sub.2 H.sub.5                                                                               7-NHCOCH.sub.3                                                                             H   CH.sub.3                                                                           CH.sub.2 CH.sub.2   Na H                    CH.sub.2 C.sub.6 H.sub.11                                                                     7-NHCOH     H   CH.sub.3                                                                           CH.sub.2 CH.sub.2   Na CN                   CH.sub.2 C.sub.6 H.sub.11                                                                     7-NHSO.sub.2 CH.sub.3                                                                      CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.2 CH.sub.2   Na CN                   C.sub.6 H.sub.11                                                                              7-NHCONHC.sub.2 H.sub.5                                                                    CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.2 CH.sub.2   Na CN                   C.sub.6 H.sub.11                                                                              5-CH.sub.3, 8-NHCOCH.sub.3                                                                 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.2 CH.sub.2   Na Cl                   C.sub.6 H.sub.5                                                                               7-NHCOC.sub.6 H.sub.5                                                                      CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.2 CH.sub.2   Na Cl                   C.sub.6 H.sub.5                                                                               7-NHCOC.sub.6 H.sub.11                                                                     CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.2 CH.sub.2   Na Br                   C.sub.6 H.sub.5                                                                               7-NHCOCH.sub.2 OH                                                                          CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.2 CH.sub.2   Na Br                   (CH.sub.2).sub.3 OCH.sub.3                                                                    7-NHCOCH.sub.2 Cl                                                                          CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.2 CH.sub.2   Na Br                   (CH.sub.3).sub.3 OCH.sub.3                                                                    7-NHCOCH.sub.2 OCH.sub.3                                                                   CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.2 CH.sub.2   Na H                    CH.sub.2 CH.sub.2 OOCCH.sub.3                                                                 7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2                                                               Na H                    CH.sub.2 CH.sub.2 OOCCH.sub.3                                                                 7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH(OH)CH.sub.2                                                                            Na H                    CH.sub.2 CH.sub.2 OH                                                                          7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH(OCOCH.sub.3)CH.sub.2                                                                   Na H                     ##STR17##     7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH(CH.sub.3)                                                                              K  H                     ##STR18##     7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH(C.sub.6 H.sub.5)                                                                       K  H                    CH.sub.2 CH.sub.2 NHCOCH.sub.3                                                                7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 N(SO.sub.2 CH.sub.3)C                                        H.sub.2 CH.sub.2 CH.sub.2                                                                          K  H                    CH.sub.2 C.sub.6 H.sub.4p-OCH.sub.3                                                           7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 N(COCH.sub.3)CH.sub.2                                         CH.sub.2           K  H                    CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                             7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 SO.sub.2 NHC.sub.2                                           H.sub.4             K  H                    CH.sub.2 CH.sub.2 CONH.sub.2                                                                  7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.2 NHSO.sub.2                                          CH.sub.2 CH.sub.2   Na H                    CH.sub.2 CH.sub.2 CN                                                                          7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.2 NHCOCH.sub.2                                         CH.sub.2           Na H                    CH.sub.2 CH.sub.3                                                                             7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 CONHC.sub.2 H.sub.4                                                              Na H                    CH.sub.2 CH.sub.3                                                                             7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 NHCOCH.sub.2                                                                     Na OC.sub.6                                                                       H.sub.5              CH.sub.2 CH.sub.2 Cl                                                                          7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 NHCONHC.sub.2                                                H.sub.4             Na H                    CH.sub.2 CH.sub.2 SO.sub. 2 C.sub.6 H.sub.5                                                   7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 N(CH.sub.3)SO.sub.2                                          C.sub.2 H.sub.4     Na H                    CH.sub.2 CH.sub.2 NHSO.sub.2 CH.sub.3                                                         7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 N(SO.sub.2 C.sub.6                                           H.sub.5)CH.sub.2 CH.sub.2 CH.sub.2                                             CH.sub.2            Na H                    CH.sub.2 CH.sub.2 N(CH.sub.3)SO.sub.2 CH.sub.3                                                7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH(SO.sub.3 K)CH.sub.2                                                                    K  H                    CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.3                                                  7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 SO.sub.2 N(CH.sub.3)C                                        .sub.2 H.sub.4      K  H                    CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.3                                                   ##STR19##  H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 SO.sub.2 N(CH.sub.3)C                                        .sub.2 H.sub.4      K  SO.sub.2                                                                       CH.sub.3             C.sub.6 H.sub.4m-CH.sub.3                                                                     7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 SO.sub.2 N(CH.sub.3)C                                        .sub.2 H.sub.4      K  H                    C.sub.6 H.sub.4m-Cl                                                                           7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 SO.sub.                                                      2 N(CH.sub.3)C.sub.2 H.sub.4                                                                       K  H                    C.sub.6 H.sub.4p-OCH.sub.3                                                                    7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 SO.sub.2 N(CH.sub.3)C                                        .sub.2 H.sub.4      K  H                    CH.sub.2 CH.sub.2 COOCH.sub.3                                                                 7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 SO.sub.2 N(CH.sub.3)C                                        .sub.2 H.sub.4      K  H                    CH.sub.2 CH.sub.3                                                                             7-CH.sub.3  H   H   CH.sub.2 CH.sub.2 SO.sub.2 N(CH.sub.3)C                                        .sub.2 H.sub.4      K  SC.sub.6                                                                       H.sub.5              C.sub.6 H.sub.5                                                                               7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 SO.sub.2 N(CH.sub.3)C                                        .sub.2 H.sub.4      K  H                    CH.sub.2 CH.sub.3                                                                             7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 SO.sub.2 N(CH.sub.3)C                                        .sub.2 H.sub.4      K  H                    C.sub.6 H.sub.11                                                                              7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 SO.sub.2 N(CH.sub.3)C                                        .sub.2 H.sub.4      K  H                    CH.sub.2 CH.sub.2 OOCC.sub.6 H.sub.5                                                          7-CH.sub.3  H   CH.sub.3                                                                           CH.sub.2 CH.sub.2 SO.sub.2 N(CH.sub.3)C                                        .sub.2 H.sub.4      K  H                    __________________________________________________________________________

                                      TABLE III                                    __________________________________________________________________________      ##STR20##                                                                                 Substituents                                                       R.sup.2     on Ring A                                                                             R.sup.5                                                                             Q             M   R.sup.4                              __________________________________________________________________________     C.sub.2 H.sub.5                                                                            None   H    CH.sub.2 CH.sub.2                                                                            K   H                                    C.sub.2 H.sub.5                                                                            None   CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   H                                    C.sub.2 H.sub.5                                                                            6CH.sub.3                                                                             H    CH.sub.2 CH.sub.2                                                                            K   H                                    C.sub.2 H.sub.5                                                                            6OCH.sub.3                                                                            CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   H                                    C.sub.2 H.sub.5                                                                            6OC.sub.4 H.sub.9n                                                                    CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   H                                    C.sub.2 H.sub.5                                                                            None   CH.sub.3                                                                            CH.sub.2 CH.sub.2 CH.sub.2                                                                   K   H                                    C.sub.2 H.sub.5                                                                            6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                         Na  H                                    C.sub.2 H.sub.5                                                                            6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2                                                 Na  H                                    H           6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2                                                         Na  H                                    H           6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                          Na  H                                    (CH.sub.2).sub.3 CH.sub.3                                                                  6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH(OH)CH.sub.2                                                                      Na  CH.sub.3                             (CH.sub.2).sub.3 CH.sub.3                                                                  6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH(OCOCH.sub.3)CH.sub.2                                                             Na  OC.sub.2 H.sub.5                     (CH.sub.2).sub.3 CH.sub.3                                                                  6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH(SO.sub.3 K)CH.sub.2                                                              K   OC.sub.2 H.sub.5                     (CH.sub.2).sub.3 CH                                                                        6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH(C.sub.6 H.sub.5)                                                                 NH.sub.4                                                                           H                                    CH.sub.2 C.sub.6 H.sub.5                                                                   6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH.sub.2 N(SO.sub.2 CH.sub.3)CH.sub.2                                 CH.sub.2      Na  H                                    CH.sub.2 C.sub.6 H.sub.5                                                                   6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH.sub.2 N(COCH.sub.3)CH.sub.2 CH                                                   Na  H                                    C.sub.2 H.sub.5                                                                            6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH.sub.2 CH.sub.2                                                                   Na  H                                    C.sub.2 H.sub.5                                                                            6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH.sub.2 CH.sub.2 NHSO.sub.2 CH.sub.2                                 CH.sub.2      K   H                                    C.sub.2 H.sub.5                                                                            6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH.sub.2 N(CH.sub.3)SO.sub.2 CH.sub.                                  CH.sub.2      K   H                                    C.sub.2 H.sub.5                                                                            6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH.sub.2 SO.sub.2 NHCH.sub.2 CH.sub.2                                               K   H                                    C.sub.2 H.sub.5                                                                            6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH.sub.2 NHCOOCH.sub.2 CH.sub.2                                                     K   H                                    C.sub.2 H.sub.5                                                                            6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH.sub.2 NHCOCH.sub.2                                                               K   CN                                   C.sub.2 H.sub.5                                                                            6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH.sub.2 NHCONCH.sub.2 CH.sub.2                                                     Na  CN                                   C.sub.2 H.sub.5                                                                            6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH(CH.sub.3)                                                                        K   CN                                   C.sub.2 H.sub.5                                                                            6CHd.sub.2 CN                                                                         CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   Cl                                   C.sub.2 H.sub.5                                                                            6CH.sub.2 OH                                                                          CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   Cl                                   C.sub.2 H.sub.5                                                                            6CH.sub.2 Cl                                                                          CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   Br                                   C.sub.2 H.sub.5                                                                            6CH.sub.2 COOCH.sub.3                                                                 CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   Br                                   C.sub.2 H.sub.5                                                                            6CH.sub.2 OC.sub.2 H.sub.5                                                            CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   Br                                   C.sub.2 H.sub.5                                                                            6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   H                                    C.sub.2 H.sub.5                                                                            6CH.sub.3                                                                             CH.sub.2 CH.sub.3                                                                   CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2                                                 K   H                                    CH.sub.2 C.sub.6 H.sub.11                                                                  6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2                                                 K   H                                    CH.sub.2 C.sub.6 H.sub.5                                                                   6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2                                                 K   H                                    C.sub.6 H.sub.11                                                                           None   CH.sub.3                                                                            CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2                                                 K   H                                    C.sub.6 H.sub.11                                                                           6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   H                                    C.sub. 6 H.sub.5                                                                           None   CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   H                                    C.sub.6 H.sub.5                                                                            6CH.sub.2 Cl                                                                          CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   H                                    C.sub.6 H.sub.5                                                                            6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH.sub.2 CH.sub.2                                                                   K   H                                    (CH.sub.2).sub.3 OCH                                                                       6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   H                                    (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 Cl                                                     6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   H                                    CH.sub.2 CH.sub.2 OOCC.sub.2 H.sub.5                                                       6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   H                                    CH.sub.2 CH.sub.2 OOCCH.sub.3                                                              6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   OC.sub.6 H.sub.5                     CH.sub.2 CH.sub.2 OH                                                                       6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   H                                    CH.sub.2 CH.sub.3                                                                          6CH.sub.3                                                                             CH.sub.2 CH.sub.2                                                                   K             H                                         ##STR21##  6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   H                                    CH.sub.2 CH.sub.2 NHCOCH.sub.3                                                             6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   H                                    CH.sub.2 C.sub.6 H.sub.4p-OCH.sub. 3                                                       6NHCOCH.sub.3                                                                         CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   H                                    CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                          6NHCOC.sub.2 H.sub.5                                                                  CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   SO.sub.2 CH.sub.3                    CH.sub.2 CH.sub.2 CONH.sub.2                                                               6NHCHO CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   H                                    CH.sub.2 CH.sub.2 CN                                                                       6NHCOCH.sub.2 CN                                                                      CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   H                                    CH.sub.2 CH.sub.2 Br                                                                       6NHCOCH.sub.2 OCH.sub.3                                                               CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   H                                    CH.sub.2 CH.sub.3                                                                          6NHCOCH.sub.2 OCH.sub.3                                                               CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   H                                    CH.sub.2 CH.sub.2 Cl                                                                       6NHCOC.sub.6 H.sub.11                                                                 CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   SC.sub.6 H.sub.5                     CH.sub.2 CH.sub.2 SO.sub.2 C.sub.6 H.sub.5                                                 6NHCOC.sub.6 H.sub.5                                                                  CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   H                                    CH.sub.2 CH.sub.2 NHSO.sub.2 CH.sub.3                                                      6Cl    CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   H                                    CH.sub.2 CH.sub.2 NHCH.sub.2 SO.sub.2 CH.sub.3                                             6NHCONHC.sub.2 H.sub.5                                                                CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   H                                    CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.3                                               6NHSO.sub.2 CH.sub.3                                                                  CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   H                                    CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.3                                               6NHCOCH.sub.2 OC.sub.6 H.sub.5                                                        CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   H                                    C.sub.6 H.sub.4m-CH.sub. 3                                                                 6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   SC.sub.2 H.sub.5                     C.sub.6 H.sub.4m-Cl                                                                        6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   H                                    C.sub.6 H.sub.4p-OCH.sub. 3                                                                6CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   H                                    CH.sub.2 CH.sub.2 COOCH.sub.3                                                              None   CH.sub.3                                                                            CH.sub.2 CH.sub.2                                                                            K   H                                    CH.sub.2 CH.sub.3                                                                          6CH.sub.3                                                                             None CH.sub.2 CH.sub.2                                                                            K   H                                    __________________________________________________________________________

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention. 

We claim:
 1. A compound having the formula ##STR22## wherein C is a coupler selected from those having the formula ##STR23## wherein R² is selected from hydrogen and the following groups: alkyl; cyclohexyl; cyclohexyl substituted with alkyl; and alkyl substituted with alkoxy, aryl, aryloxy, cyclohexyl, cyano, alkanoyloxy, alkoxycarbonyl, alkoxycarbonyloxy, aroyloxy, alkylcarbamoyloxy, arylcarbamoyloxy, or with a group having the formula ##STR24## wherein R⁷ is hydrogen, alkyl or aryl;R⁸ is hydrogen or alkyl; R⁷ and R⁸ collectively are --(CH₂)₅ -- or --CH₂ CH₂ OCH₂ CH₂ --; R⁹ is alkanoyl or aroyl; R¹⁰ is hydrogen, alkyl, aryl or cyclohexyl; R¹¹ is ethylene, propylene, trimethylene, o-cyclohexylene, or o-arylene, or when Y is --CO--, R¹¹ also can be --NHCH₂ --, --N(lower alkyl)CH₂ --, --SCH₂ --, --OCH₂ -- or --CH₂ OCH₂ --; Y is --CH₂ --, --CO--, or --SO₂ --; and R¹² is aryl, benzyl, cyclohexyl, 1,2,4-triazol-3-yl, or 2-benzothiazolyl; R⁴ represents one or two substituents each of which is selected from hydrogen, halogen, cyano, alkyl, alkylsulfonyl, arylsulfonyl, arylthio, cyclohexylthio, alkoxy, aryloxy, 2-benzothiazolylthio, 2-thiazolylthio, 2-thiadiazolylthio, 2-oxadiazolylthio, 1,2,4-triazol-3-ylthio, 2-pyrimidinylthio, and such groups substituted with up to three of halogen, OH, aryl, CN, alkoxy, alkanoyl, aroylamino, alkylamino, alkanoyloxy, carbamoyl, alkylcarbamoyl, sulfamyl, alkylsulfonyl, succinimido, or alkoxycarbonyl groups; each ring A of the couplers is unsubstituted or substituted with up to three substituents selected from alkyl, alkoxy, halogen, NHSO₂ -alkyl, NHCOR₁ or such groups substituted with up to three of halogen, OH, aryl, CN, alkoxy, alkanoyl, aroylamino, alkylamino, alkanoyloxy, carbamoyl, alkylcarbamoyl, sulfamyl, alkylsulfonyl, succinimido, or alkoxycarbonyl groups, wherein R₁ is hydrogen, alkyl, alkoxy, alkylamino, aryl, cyclohexyl, furyl, cycloalkyl, or such groups substituted with up to three of halogen, OH, aryl, CN, alkoxy, alkanoyl, aroylamino, alkylamino, alkanoyloxy, carbamoyl, alkylcarbamoyl, sulfamyl, alkylsulfonyl, succinimido, or alkoxycarbonyl groups; R₃ is selected from hydrogen; alkyl; alkyl substituted with alkoxy, alkoxyalkoxy, aryl, cycloalkyl, cyano, CONRR, SO₂ NRR, SO₃ M, aryloxy, cyclohexoxy, ##STR25## 2-pyrrolidono, furyl, alkylthio, or alkylsulfonyl wherein each R is independently selected from hydrogen, alkyl, and alkyl substituted with halogen, hydroxy, phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, or alkoxy; alkylcarbamoyl; alkenyl; aryl; cycloalkyl; and alkylycloalkyl; R₅ and R₆ are each independently selected from hydrogen, alkyl, and alkyl substituted with up to three of halogen, OH, aryl, CN, alkoxy, alkanoyl, aroylamino, alkylamino, alkanoyloxy, carbamoyl, alkylcarbamoyl, sulfamyl, alkylsulfonyl, succinimido, or alkoxycarbonyl groups; Q is selected from alkylene of 2-8 carbons, alkylene of 2-8 carbons substituted by one to three groups selected from --OH, --OCOCH₃, --C₆ H₅, and --SO₃ K, and alkylene of 2-8 carbons which contain in its chain one to three groups selected from --O--, --SO₂ --, --S--, --N(SO₂ CH₃)--, --N(COCH₃)--, --NHSO₂ --, --N(CH₃)SO₂ --, --SO₂ NH--, --NHCOO--, --NHCO--, --NHCONH--, and --N(SO₂ C₆ H₅)--; and M is H⁺, Na⁺, K⁺, or NH₄ ⁺.
 2. The compound according to claim 1 having the formula ##STR26##
 3. The compound according to claim 1 having the formula ##STR27##
 4. The compound according to claim 1 having the formula ##STR28## 